US4626519A - Supported polyolefin catalyst components and methods of making and using same - Google Patents

Supported polyolefin catalyst components and methods of making and using same Download PDF

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US4626519A
US4626519A US06/773,164 US77316485A US4626519A US 4626519 A US4626519 A US 4626519A US 77316485 A US77316485 A US 77316485A US 4626519 A US4626519 A US 4626519A
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solid
process according
extraction
catalyst
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Nemesio D. Miro
Floyd E. Farha
Charles E. Capshew
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Mallinckrodt Chemical Inc
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Phillips Petroleum Co
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Assigned to PHILLIPS PETROLEUM COMPANY A DE CORP reassignment PHILLIPS PETROLEUM COMPANY A DE CORP ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: FARHA, FLOYD E.
Assigned to PHILLIPS PETROLEUM COMPANY A DE CORP reassignment PHILLIPS PETROLEUM COMPANY A DE CORP ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: CAPSHEW, CHARLES E., FARHA, FLOYD E., MIRO, NEMESIO D.
Priority to US06/773,164 priority Critical patent/US4626519A/en
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Assigned to PHILLIPS PETROLEUM COMPANY A DE CORP reassignment PHILLIPS PETROLEUM COMPANY A DE CORP ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: CAPSHEW, CHARLES E., FARHA, FLOYD E., MIRO, NEMESIO D.
Priority to CA512377A priority patent/CA1262344C/fr
Priority to ZA866255A priority patent/ZA866255B/xx
Priority to AU61760/86A priority patent/AU572031B2/en
Priority to JP61201191A priority patent/JPS6289707A/ja
Priority to EP86112069A priority patent/EP0214590A3/fr
Priority to NO863561A priority patent/NO167209C/no
Priority to ES8601673A priority patent/ES2001126A6/es
Priority to US06/917,749 priority patent/US4680351A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

  • the present invention relates to a novel catalyst for the polymerization of olefins.
  • the invention relates to the use of said catalyst in the polymerization of olefins.
  • Organometallics have been used in combination with transition metal compounds to catalyze the production of high molecular weight polymers from ethylene and alpha-olefins to produce polymers having high stereoregularity.
  • the basic catalysts used in these methods are formed by combining a transition metal salt with a metal alkyl or hydride. Titanium trichloride and an aluminum alkyl, such as triethyl aluminum or diethyl aluminum chloride, are often used. However, such catalysts generally have low productivity and produce polymer with low stereoregularity.
  • Isotactic polypropylene results from a head-to-tail linkage of the monomer units resulting in the asymmetric carbon atoms all having the same configuration.
  • the isotactic index is a measure of the precentage of isotactic isomer in the polymer.
  • Atactic polypropylene results from random linkage of the monomer units.
  • Isotactic polypropylene is a highly useful commercial product having high tensile strength, hardness, stiffness, resilience, clarity and better surface luster. Polypropylene finds extensive commercial use in injection molding, film, sheeting, filament and fiber applications. Commercially useful polypropylene contains essentially the stereoregular or isotactic isomer.
  • the polymer produced using these basic catalysts must be extracted to remove the atactic (non-stereoregular) polymer to increase the percentage of isotactic (stereo-regular) polymer in the final product. It is also necessary to deash polymer produced by this method to remove catalyst residues. The additional production steps of polymer extraction and polymer deashing add significantly to the cost of polymer produced with these basic catalysts.
  • a particularly useful high activity catalyst is disclosed in U.S. Pat. No. 4,347,158, the disclosure of which is incorporated herein by reference.
  • One particularly preferred embodiment of the invention of that patent involves a solid titanium-containing catalyst component prepared by the co-comminution of magnesium chloride, aluminum chloride, an aromatic ester, an aromatic ether, and titanium tetrachloride.
  • the catalyst of the present invention comprises the solid product prepared by
  • the percentages are based on the weight of aluminum rather than the weight of the solid catalyst. In other words, it is required that at least 5 weight percent of the aluminum, calculated as elemental metal, be removed from the coground solid by the extraction and separation steps.
  • the amount of Al removed can be determined by determining the amount of Al that is in the liquid after the separation of the solid from the liquid.
  • the catalyst is also contacted with additional polymerization active metal either after or simultaneous with the extraction.
  • co-comminuting is used herein to refer to the co-grinding or co-pulverization of the components. This term is used to distinguish over a simple mixing which does not result in any substantial alteration of the particle size of the components of the mixture.
  • the support base can be viewed as forming the nucleus of the catalyst.
  • the salts referred to above for use as the support base are the halogen-containing compounds of magnesium, manganese, zinc, and calcium.
  • Specific examples of such compounds include magnesium chloride, magnesium bromide, manganese chloride, manganese bromide, calcium chloride, zinc chloride, magnesium hydroxychloride, complexes of the same with trialkylaluminums such as triethylaluminum, and complexes of the above with electron donors.
  • the best support bases are the salts of magnesium and manganese.
  • Typical examples of such salts include the magnesium and manganese dihalides, alkyloxides, aryloxides, and combinations thereof.
  • the preferred support bases are M(OR) n X 2-n where M is magnesium or manganese, R is an alkyl or aryl radical, X is a halide or pseudohalide and n is 0, 1, or 2.
  • Some typical examples of salts having such formula are MgCl 2 , MgBr 2 , MgF 2 , Mg(OCH 3 ) 2 , Mg(OCH 2 CH 3 ) 2 , Mg(OC 6 H 5 ) 2 . It is within the scope of the invention to employ mixtures of such salts.
  • the currently most preferred embodiments employ magnesium halides, especially magnesium dichloride.
  • magnesium chloride is used as a support base it should preferably be substantially anhydrous.
  • Anhydrous magnesium chloride may be prepared by drying under an HCl blanket at a temperature of 350° C.
  • a dehydrating agent such as the silicon tetrahalides or calcium hydride may be added to and co-comminuted with a water containing support base prior to production of the catalyst component.
  • the dehydrating agent becomes a part of the support base.
  • silicon tetrachloride is used for this purpose. Silicon tetrachloride effectively dehydrated a water containing magnesium chloride support base and surprisingly had no apparent effect on the activity of the resulting catalyst. It is preferred that the molar ratio of dehydrating agent to water present in the support base be about one to one.
  • aluminum halide is used to refer to aluminum compounds having at least one halogen bonded directly to the aluminum.
  • Examples include AlCl 3 , Al-dichloro-phenoxy, Al-mono-chloro-diphenoxy, Al-dichloro-xylenoxy, Al-mono-chloro-dixylenoxy, Al-dichloro-2,6-t-butyl-p-cresoxy, Al-dichloro-octoxy, Al-monoethyl-dichloride, Al-siloxyl-chloride, and the like.
  • electron donors include organic compounds having at least one atom of oxygen, sulfur, nitrogen, or phosphorus to function as the electron donor. More specifically, the term electron donor is used to include ethers, esters, ketones, aldehydes, alcohols, carboxylic acids, phenols, thioethers, thioesters, thioketones, amines, amides, nitriles, isocyanates, phosphites, phosphoryl compounds, and phosphines. Typically it is preferred to use compounds having no more than 16 carbon atoms per molecule. It is currently believed that aromatic ethers and the esters of aromatic acids are the most useful electron donors.
  • both an aromatic ester and an aromatic ether are employed.
  • the more common esters are those derived from carboxylic acids having 1 to 12 carbon atoms and alcohols having 1 to 12 carbon atoms.
  • the more common ethers are those containing 2 to 12 carbon atoms and 1 to 10 ether oxygen atoms.
  • Typical examples of the aromatic esters include the alkyl and aryl esters of aromatic carboxylic acids such as benzoic, toluic, p-methoxybenzoic, and phthalic acid. Some specific examples include ethyl benzoate, methyl benzoate, methyl-p-toluate, ethyl-p-toluate, and methyl-anisate.
  • aromatic ethers is intended to include those ethers having two aromatic groups as well as those having one aromatic group and one alkyl group.
  • Some specific examples include anisole, phenetole, diphenyl ether, phenylallyl ether, and benzofuran.
  • the currently most preferred combination is ethyl benzoate and anisole.
  • the transition metal is generally selected from the group consisting of titanium, vanadium, chromium and zirconium. In the preferred embodiment, the transition metal is tetra-valent titanium.
  • transition metal compound within the above formula will depend upon the reaction conditions and other constituents present in the catalyst.
  • Some examples of transition metal compounds having polymerization activity are TiCl 4 , Ti(OCH 3 )Cl 3 , Ti(OCH 2 CH 3 )Cl 3 , VCl 3 , VOCl 2 , VOCl 3 and VO(OCH 3 )Cl 2 .
  • liquid titanium tetrachloride is used as the active transition metal compound.
  • the molar ratio of the support base to the aluminum chloride is in the range of about 8/1 to 8/2, more preferably in the range of about 8/1 to 8/1.5.
  • the molar ratio of the support base to the electron donor would typically be in the range of about 8/0.5 to 8/3, more preferably in the range of about 8/1 to 8/3.
  • the molar ratio of the support base to the transition metal compound would typically be in the range of about 8/0.1 to 8/1, more preferably about 8/0.4 to 8/0.6.
  • aromatic ester is typically employed in a molar amount at least equivalent to that of the coground transition metal compound. More typically, the molar ratio of the aromatic ester to the transition metal compound would be in the range of about 1.5/1 to 3/1.
  • the co-comminution of the components can be carried out in any order.
  • the components can be added one at a time with additional comminution with each newly added component or several of the components can be combined first and comminuted simultaneously. It is also possible to combine some of the components before combining them with a comminuted product.
  • the currently favored technique involves co-comminuting the support base and the aluminum halide, then co-comminuting that product with electron donor, and then co-comminuting that product with the transition metal compound.
  • the preferred method of producing the above catalyst component comprises the co-comminution of the constituents under an inert atmosphere in a ball or vibration mill.
  • the support base is initially charged into the mill. If the support base contains water which must be removed, a sufficient quantity of dehydrating agent is initially added to the support base and the resulting mixture co-comminuted at temperatures between about 0° C. and about 90° C. for from about 15 minutes to about 48 hours. Preferably this mixing is for from about 6 hours to about 24 hours, optimally for about 15 hours, at temperatures between about 35° C. and about 50° C.
  • the preferred mixing temperature is from about 25° C. to about 50° C., a temperature of 30° C. being particularly preferred.
  • Mixing times may range from about 15 minutes to about 48 hours. Preferred mixing times are from about 12 hours to about 20 hours, with optimal mixing at about 16 hours. Insufficient mixing will not yield a homogeneous compound, while overmixing may cause agglomeration or may significantly decrease particle size of the catalyst component, causing a direct reduction in particle size of the polypropylene produced from the catalyst component.
  • a support base containing water, the dehydrating agent and the aluminum halide are charged into the ball or vibration mill together and co-comminuted at temperatures between about 0° C. and about 90° C. for from about 15 minutes to about 48 hours.
  • this mixing is for from about 12 hours to about 20 hours, optimally about 16 hours, at temperatures between about 35° C. and about 50° C.
  • a first electron donor is co-comminuted with the support base, aluminum halide and dehydrating agent, if used, to produce an enhanced support.
  • Mixing may be at temperatures between about 0° C. and about 90° C. for from about 30 minutes to about 48 hours.
  • the preferred mixing temperatures are from about 25° C. to about 50° C. for from about one hour to about 5 hours.
  • the active transition metal compound To the enhanced support produced as described above is added the active transition metal compound. Although many transition metal compounds of the formula MO p (OR) m X n-2p-m as described above will provide satisfactory catalyst components, liquid titanium tetrachloride in the preferred active compound. Such an active transition metal compound is added to the ball or vibration mill and co-comminuted therein with the enhanced support. This mixing may be at temperatures from about 0° C. to about 90° C. and for from about 15 minutes to about 48 hours. It is preferred that this mixing take place at temperatures ranging from about 25° C. to about 50° C. and for from about 12 hours to about 20 hours, optimally for about 16 hours, to produce the supported high efficiency catalyst component.
  • a second electron donor which may be different from or the same as the first electron donor may be co-comminuted with the enhanced support prior to addition of the active transition metal compound.
  • the molar ratio of the support base to the second electron donor would typically be in the range of about 8/0.5 to 8/3, more preferably about 8/1 to 8/1.5.
  • ethyl benzoate is employed to make the enhanced support and then anisole is co-comminuted in the ball or vibration mill with the enhanced support at temperatures from about 0° C. to about 90° C. for from about 15 minutes to about 48 hours prior to addition of titanium tetrachloride.
  • the preferred mixing is at from about 25° C. to about 50° C. for from about one hour to about 5 hours, optimally about 3 hours.
  • the electron donor i.e., ethyl benzoate
  • the active transition metal compound e.g., titanium tetrachloride
  • This complex is then mixed with the support under the conditions and for the time specified above for the active transition metal compound.
  • solids that basically act as solid diluents.
  • solids include lead dichloride, tin dichloride, aluminum oxide, silicium oxide, tin oxides, titanium dioxide, zirconium dioxide, aluminum sulphate, aluminum stearate, aluminum phosphate, durene, hexamethylbenzene, anthracene, naphthalene, biphenyl and phenanthrene, and the like.
  • the solid obtained as described above is then contacted with a liquid under conditions sufficient to extract aluminum from the solid.
  • the extent of the extraction can vary depending upon the extent of activity desired. Typically it is preferred to extract to provide a reduction in aluminum of at least 10%, more preferably at least 25%, and still more preferably in the range of about 35-50%, by weight, based on the amount of Al in the coground solid.
  • the extraction is carried out to give substantially optimum activity.
  • the slurry is stirred during the extraction.
  • the amount of extraction liquid employed can vary but, typically, it would be employed in such an amount that the resulting slurry would contain about 15 to about 60 weight percent solids based on the weight of the liquid, more preferably about 25 to about 50 weight percent.
  • the actual temperature and time for the extraction can vary depending upon the results desired. Typically the extraction would be conducted at a temperature in the range 30° C. to about 120° C. Generally, however, the temperature should be kept below the boiling point of the liquid having the lowest boiling point. It is currently preferred to use a temperature in the range of about 70° C. to about 100° C., more preferably 90° C. to 100° C. At this temperature when the solid catalyst is employed in an amount equal to about 25 to 35 percent of the weight of the liquid, it is currently preferred to contact the catalyst with the liquid at a temperature in the range of about 90° C. to about 100° C. for about 1 to 6 hours, most preferably about 2 hours.
  • Any suitable organic compounds can be employed as the extraction liquid. It is, however, currently preferred to employ organic compounds that are liquid at temperatures in the range of 25° C. to 35° C.
  • the currently preferred compounds are hydrocarbons. Some typical examples include heptane, pentane, 2,3-dimethylpentane, hexane, benzene, toluene, xylene, and ethyl benzene. It is currently preferred to use a combination of aromatic and paraffinic hydrocarbons, i.e., heptane and toluene.
  • the results obtained will vary depending upon the specific extraction liquid employed.
  • the toluene generally would account for about 2.5 to 75 weight percent of the liquid. More preferably, the toluene would be about 30 to about 60 weight percent of the liquids.
  • the solid is separated from the liquid.
  • the liquid In order to maximize the removal of soluble components it is preferred to carry out the extraction with the liquid at a temperature greater than 30° C. Most preferably the separation is made while the liquid is still at about the same temperature that was used in the extraction.
  • the solids can be removed from the liquid using any suitable conventional technique. Examples include decanting and filtering. Typically it is preferred that the separation be conducted under such conditions that at least 10 weight percent of the aluminum is removed from the solid, still more preferably at least 25 weight percent, and most preferably about 35 to 50 weight percent.
  • the resulting solid can be used as a catalyst.
  • it would be washed moderately with an organic liquid, for example a paraffinic or aromatic hydrocarbon.
  • an organic liquid for example a paraffinic or aromatic hydrocarbon.
  • the washing can be carried out at normal ambient temperature, e.g., 20° C. to 35° C., although elevated temperature can be employed.
  • a polymerization active transition metal compound as described above is included in the extraction mixture.
  • transition metal compounds of the formula given above can be employed, it is currently preferred to employ liquid titanium tetrachloride.
  • the additional transition metal compound is generally employed in such an amount that the total transition metal, including that in the ground solid, would be equal to about 1 to about 20 weight percent of the solid, more preferably about 2 to about 10 weight percent.
  • the amount of transition metal compound in the liquid When used in the extraction liquid the amount of transition metal compound in the liquid would generally be in the range of about 1 to about 20 weight percent based on the weight of the liquid, more preferably about 5 to 15 weight percent.
  • this contacting of solid with additional transition metal would be conducted at a temperature in the range of 30° C. to 120° C., which is below the boiling point of the components of the slurry. It is currently preferred to use a temperature in the range of about 70° C. to about 100° C., more preferably about 90° C. to 100° C.
  • the length of contacting for optimum results can be readily determined by routine experimental. Currently, it is preferred to carry out the contacting for about 1 to about 3 hours, more typically about two hours. After that the solid and the liquid are separated, preferably while the liquid is hot, and most preferably at about the same temperature used in the contacting.
  • the contacting with the transition metal containing liquid and the separation can be repeated one or more times.
  • the recovered solid can be used as recovered; however, it is generally preferred to wash it with an organic liquid until substantially all free transition metal compound has been washed off the solid.
  • the wash liquid can be any suitable organic liquid, typically a paraffinic or aromatic hydrocarbon. Examples include heptane, hexane, xylenes and toluene.
  • the solid is subjected to at least two separate extractions with fresh portions of the transition metal-containing aromatic/paraffinic mixture. Hydrocarbon washing between the extractions is not absolutely necessary but is currently preferred.
  • organic liquid which is free of transition metal and then to contact the resulting solid with a hot organic liquid containing an active transition metal compound.
  • suitable organic liquids include any of those set forth above as being suitable for use in forming the extraction liquid. Either a single liquid compound or a mixture of compounds forming a liquid can be employed. The amount of transition metal in the liquid would be as described above for the transition metal-containing extraction liquid.
  • the solid obtained from the above-described embodiments can be used directly as a catalyst, but more typically is stored in an organic liquid of the type generally used in the polymerization of olefins.
  • organic liquids include hexane, heptane, and mineral oil. Paraffinic hydrocarbons are particularly preferred.
  • the catalyst component produced by the foregoing methods is preferably used in conjunction with a co-catalyst of an organometallic compound and optimally another organic electron donor when it is desired to produce stereoregular polyolefins.
  • the organometallic co-catalyst is selected from the group consisting of the alkyl aluminums, the alkyl aluminum halides and the alkyl aluminum hydrides.
  • the preferred co-catalyst is triethyl aluminum, triisobutyl aluminum or diethyl aluminum chloride, with triethyl aluminum especially preferred.
  • the molar ratio of organometallic co-catalyst to titanium-containing catalyst component, preferably moles of triethyl aluminum to gram-atoms of Ti in the catalyst component of the present invention may range up to about 400 to one. In laboratory liquid pool polymerization the range of about 150-300 to one is preferred, with about 240 to one especially preferred. In continuous production processes, a range of about 30-100 to one is presently believed to be preferred.
  • the electron donor for use in the cocatalyst is selected from the same group as the electron donors described for making the catalyst component and may be the same or different therefrom.
  • Preferred electron donors are selected from the esters of aromatic acids such as ethyl anisate, methyl p-anisate, methyl p-toluate or ethyl benzoate.
  • the most preferred electron donor is methyl p-toluate.
  • the preferred molar ratio of organometallic co-catalyst to electron donor component, preferably moles of triethyl aluminum to moles of methyl p-toluate of the present invention is about 1.0-20.0 to one, most preferably about 2.0-3.5 to one.
  • the cocatalyst comprises an organoaluminum compound as described above, a silicon compound of the general formula ##STR1## wherein R 3 , R 4 and R 5 are each a hydrocarbon radical having 1 to 24 carbon atoms, alkoxy, hydrogen, or halogen, R 6 is a hydrocarbon radical having 1 to 24 carbon atoms and q is 1 ⁇ q ⁇ 30; and another electron donor which is capable of forming a complex with the organoaluminum compound.
  • silicon compounds include monomethyl tri-methoxy silane, monomethyl triethoxy silane, monomethyl tri-n-butoxy silane, monomethyl tri-sec-butoxy silane, monomethyl triisopropoxy silane, monomethyl tripentoxy silane, monomethyl trioxtoxy silane, monomethyl tristearoxy silane, monomethyl triphenoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, dimethyl diisopropoxy silane, dimethyl diphenoxy silane, trimethyl monomethoxy silane, trimethyl monoethoxy silane, trimethyl monoisopropoxy silane, trimethyl monophenoxy silane, monomethyl dimethoxy monochlorosilane, monomethyl diethoxy monochlorosilane, monomethyl diethoxy monochlorosilane, monomethyl diethoxy monobromosilane, monomethyldiphenoxy monochlorosilane, dimethyl monoethoxy monochlorosilane, monoethyl trimethoxy silane, trimethyl trimethoxy
  • Examples of electron donors capable of forming complexes with organoaluminum compounds include alkyl and aryl esters of aromatic carboxylic acids, such as, for example, benzoic, toluic, p-methoxybenzoic and phthalic acids. Some representative examples include ethyl benzoate, ethyl p-toluate, n-octyl phthalate, methyl p-toluate, diisobutyl phthalate, methy para anisate. Other examples include ethers such as anisole, phosphites such as triethyl-phosphite, and compounds such as tri-allyl-isocyanurite.
  • aromatic carboxylic acids such as, for example, benzoic, toluic, p-methoxybenzoic and phthalic acids.
  • Some representative examples include ethyl benzoate, ethyl p-toluate, n-octyl phthalate, methyl p-toluate,
  • An especially preferred cocatalyst composition of the combination of a trialkyl aluminum, a hydrocarbyl trialkyoxy silane, and an alkyl ester of an aromatic carboxylic acid include the combination of triethylaluminum and phenyl triethoxy silane with methyl para toluate, or methyl para anisate, or ethyl benzoate.
  • the molar ratio of the silane donor to the other donor will be in the range of about 0.3/1 to about 1.5/1 and the molar ratio of the alkyl aluminum compound to the total electron donors would generally be in the range of about 2/1 to 3.5/1.
  • a catalyst produced by the foregoing method may be used in standard methods for polymerization of alphaolefins.
  • the catalyst may be used in liquid pool, inert solvent or gas phase preparations.
  • the preferred catalyst of the present invention produce polypropylene having an isotactic index of at least 80, more preferably 90, and most preferably 93 or greater, a total ash content of not more than about 700 ppm, but more preferably as low as about 300 ppm, and a magnesium residue of less than about 20 ppm.
  • Olefin polymerizing conditions generally involve temperature in the range of 20° C. to 120° C., more typically 50° C. to 100° C., and pressures in the range of atmospheric to 70 kg/cm 2 ; more typically in the range of 2 to 60 kg/cm 2 .
  • the preferred means of using the catalyst of the present invention is in liquid pool polymerization. When so used, in the preparation of polypropylene, the expensive steps of polymer extraction, polymer deashing and the associated solvent recovery are eliminated.
  • one or more olefins having from about 2 to 18 carbon atoms may be polymerized according to the present invention.
  • olefins are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-methyl-1-heptene, 5-methyl-1-heptene, 6-methyl-1-heptene, and 4,4-dimethyl-1-hexene.
  • Such 1-olefins may be copolymerized with monomers copolymerizable therewith such as vinyl acetate and lower alkyl (C 1 to C 12 alkyl) acrylic esters.
  • monomers copolymerizable therewith such as vinyl acetate and lower alkyl (C 1 to C 12 alkyl) acrylic esters.
  • Particularly preferred olefins which are intended to be polymerized according to the present invention are ethylene, propylene, 1-butene and 1-hexene.
  • the titanium-containing solid product that is subjected to treatment with various liquids is the product of the co-comminution of anhydrous magnesium chloride, aluminum trichloride, ethyl benzoate, anisole, and TiCl 4 .
  • a typical procedure which can be used for making such a solid involves cogrinding the components in a nitrogen purged 125 liter Vibratom mill containing 0.3470 pounds of 1.0" dia. steel balls. To the mill there is charged about 68.75 pounds of anhydrous MgCl 2 and about 12.02 pounds of AlCl 3 . The mixture is milled for 16 hours at 28°-32° C. Then while the milling at 28°-32° C.
  • Catalyst A was employed in the polymerization of propylene using a cocatalyst comprising triethylaluminum (TEA) and methyl-p-toluate (MPT) at mole ratios of 3/1 and 3.4/1.
  • TEA triethylaluminum
  • MPT methyl-p-toluate
  • Catalyst B was prepared by forming a 50/50 weight ratio slurry of Catalyst A in heptane. The mixture was agitated and 15.7 weight % TiCl 4 based on the heptane was added. The mixture was heated to 90°-95° C. and agitated for several hours. After the heating period the slurry was cooled rapidly. Once the slurry had cooled to about ambient temperature the liquid was removed by decanting to leave a solid Catalyst B. The relative effectiveness of these catalysts in the polymerization of propylene was as follows:
  • This example sets forth a comparison of the polymerization results obtained using another base catalyst, referred to here as Catalyst C.
  • Catalyst D In one procedure a portion of Catalyst C was washed and filtered nine times at 90° to 95° C. with heptane and then vacuum dried to give a Catalyst D.
  • Catalyst D was suspended in heptane to give a slurry containing 50 weight percent Catalyst D.
  • the mixture was agitated and 15.7 weight % TiCl 4 , based on the weight of the heptane, was added.
  • the mixture was then heated to 90°-95° C. and agitated for several hours.
  • the slurry was then rapidly cooled and then the liquid decanted off to give Catalyst E.
  • Catalyst F a portion of base Catalyst C was washed once with heptane at 90°-93° C. and the solid removed from the liquid by filtering at 90°-93° C. The resulting solid was then contacted with TiCl 4 in the same manner as used in main Catalyst D. The resulting solid is referred to here as Catalyst F.
  • Catalysts E and F results in productivities that are at least about 1000 kg/g higher than those provided by Catalyst B of Example I.
  • the catalysts were prepared in clean 100 ml or one pint size septum bottles which had been thoroughly dried. Inside the dry box, 15-30 grams of Base Catalyst G and a clean magnetic stirring bar were loaded into the bottle. The bottle was capped and filled with the required amount of TiCl 4 and liquids by means of a syringe or a cannula transfer needle. The mixture was heated with a hot bath and kept at 95°-100° C. while stirring for several hours.
  • the recovered solids were moderately washed with 75-150 ml of room temperature heptane and then slurried in heptane.
  • the resulting catalysts were then evaluated for use in the polymerization of propylene.
  • a 1-gallon Autoclave Engineers, Inc. reactor was used. The reactor was conditioned prior to each polymerization by filling with 2 liters heptane and heating to 176° C. for 15 minutes. The heptane was drained hot and the reactor cooled to room temperature with tap water through the jacket. Under a propylene purge, the reactor was sequentially charged with TEA, MPT, and catalyst. The mole ratio of TEA to MPT was about 3/1. The reactor was sealed and hydrogen was added by measuring the pressure drop from a 300 ml vessel. About 3-liters of propylene was metered into the reactor and the contents stirred while being heated from room temperature to 70° C.
  • the propylene reservoir was heated to achieve a 600 psi vapor pressure.
  • Propylene was slowly added to the reactor while maintaining 69°-71° C. temperature.
  • the propylene feed was left open and polymerization temperature was kept at 70° C. for one hour, unless otherwise specified.
  • the propylene feed was cut off while some propylene was drained down the bottom of the reactor where it is collected in a preweighed 1-gallon can. This makes room for the addition of 5 ml methanol, injected into a holding vessel and carried to the reactor through the propylene feed. Finally, all of the propylene was drained down the bottom of the reactor, followed by a 2-liter propylene used in washing the polymer. The liquid propylene was evaporated and, after drying in a vacuum oven, the soluble polymer was measured. The polypropylene was stabilized and then dried in a vacuum oven. Productivity was based on the total polymer (kg of polymer/g of solid catalyst/hr).
  • Another set of catalysts were prepared using different techniques of treating the base catalyst.
  • a catalyst was prepared by placing 10 grams of the base catalyst in a flask in a dry box. Then 100 ml of TiCl 4 was added and the resulting slurry was stirred for 2 hours at 80°-85° C. While the mixture was hot the solid was separated from the liquid by filtering. A portion of the recovered solid was contacted with another 100 ml of TiCl 4 and heated and filtered, and then dried to give Catalyst M.
  • a catalyst is viewed as performing better if its productivity is higher at equivalent II or vice versa, or if both productivity and II are higher.
  • Table VI shows that invention catalysts O-Q give a better overall balance of productivity/II/bulk density.
  • a comparison of Tables VI-VIII shows that in all catalysts, the use of a mixed MPT/PTES gives a superior performance compared to the use of either MPT or PTES alone.
  • Comparative Catalyst M obviously carried a significant amount of soluble titanium and as a result it gave a lower %II than the other catalysts with each cocatalyst system.

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US06/773,164 1985-09-06 1985-09-06 Supported polyolefin catalyst components and methods of making and using same Expired - Lifetime US4626519A (en)

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US06/773,164 US4626519A (en) 1985-09-06 1985-09-06 Supported polyolefin catalyst components and methods of making and using same
CA512377A CA1262344C (fr) 1985-09-06 1986-06-25 Constituants de catalyseur sur support pour la polymerisation olefinique; methodes de preparation et d'utilisation
ZA866255A ZA866255B (en) 1985-09-06 1986-08-19 Supported polyolefin catalyst components and methods of making and using same
AU61760/86A AU572031B2 (en) 1985-09-06 1986-08-22 Supported polyolefin catalyst
JP61201191A JPS6289707A (ja) 1985-09-06 1986-08-27 オレフインの重合用触媒の製造方法
EP86112069A EP0214590A3 (fr) 1985-09-06 1986-09-01 Composant de catalyseur supporté pour polymérisation d'oléfines et méthodes pour le préparer et l'utiliser
NO863561A NO167209C (no) 1985-09-06 1986-09-05 Katalysator og polymerisering av alkener ved anvendelse av katalysatoren.
ES8601673A ES2001126A6 (es) 1985-09-06 1986-09-05 Un procedimiento para preparar un catalizador adecuado para uso en la polimerizacion de olefinas
US06/917,749 US4680351A (en) 1985-09-06 1986-10-10 Supported polyolefin catalyst components and methods of making and using same

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Cited By (2)

* Cited by examiner, † Cited by third party
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US5106807A (en) * 1990-01-10 1992-04-21 Himont Incorporated Components and catalysts for the polymerization of olefins
US6133386A (en) 1997-01-08 2000-10-17 Hercules Incorporated Metal oxide solid acids as catalysts for the preparation of hydrocarbon resins

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100564400C (zh) * 2001-05-29 2009-12-02 联合碳化化学及塑料技术有限责任公司 烯烃聚合催化剂组合物和制备方法
JPWO2009005074A1 (ja) * 2007-06-29 2010-08-26 東邦チタニウム株式会社 オレフィン類重合用固体触媒成分、その製造方法および触媒並びにこれを用いたオレフィン類重合体の製造方法

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US3492281A (en) * 1967-06-29 1970-01-27 Goodyear Tire & Rubber Process for the polymerization of diolefins with beta titanium trichloride and organoaluminum compounds
US3850899A (en) * 1970-06-15 1974-11-26 Mitsui Petrochemical Ind Process for polymerizing olefins and catalyst therefor
US4127505A (en) * 1975-11-25 1978-11-28 Toa Nenryo Kogyo Kabushiki Kaisha Process for the production of a catalyst component for use in the polymerization of α-olefins
US4347158A (en) * 1980-05-02 1982-08-31 Dart Industries, Inc. Supported high efficiency polyolefin catalyst component and methods of making and using the same
EP0101615A2 (fr) * 1982-08-20 1984-02-29 Phillips Petroleum Company Composants de catalyseur sur support pour polyoléfines, procédé de préparation et utilisation de ceux-ci
US4555496A (en) * 1982-08-20 1985-11-26 Phillips Petroleum Company Supported polyolefin catalyst components and methods of making and using the same

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NL8201574A (nl) * 1982-04-15 1983-11-01 Stamicarbon Werkwijze voor het bereiden van een vaste katalytische titaankomponent en werkwijze voor het polymeriseren van alkenen-1 onder toepassing van een dergelijke titaankomponent.

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US3135889A (en) * 1962-05-22 1964-06-02 Jack A Soules Protected window x-ray tube
US3492281A (en) * 1967-06-29 1970-01-27 Goodyear Tire & Rubber Process for the polymerization of diolefins with beta titanium trichloride and organoaluminum compounds
US3850899A (en) * 1970-06-15 1974-11-26 Mitsui Petrochemical Ind Process for polymerizing olefins and catalyst therefor
US4127505A (en) * 1975-11-25 1978-11-28 Toa Nenryo Kogyo Kabushiki Kaisha Process for the production of a catalyst component for use in the polymerization of α-olefins
US4347158A (en) * 1980-05-02 1982-08-31 Dart Industries, Inc. Supported high efficiency polyolefin catalyst component and methods of making and using the same
EP0101615A2 (fr) * 1982-08-20 1984-02-29 Phillips Petroleum Company Composants de catalyseur sur support pour polyoléfines, procédé de préparation et utilisation de ceux-ci
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US5106807A (en) * 1990-01-10 1992-04-21 Himont Incorporated Components and catalysts for the polymerization of olefins
US6133386A (en) 1997-01-08 2000-10-17 Hercules Incorporated Metal oxide solid acids as catalysts for the preparation of hydrocarbon resins
US6281309B1 (en) 1997-01-08 2001-08-28 Eastman Chemical Company Flourinated solid acids as catalysts for the preparation of hydrocarbon resins
US6310154B1 (en) 1997-01-08 2001-10-30 Eastman Chemical Company Solid acids as catalysts for the preparation of hydrocarbon resins
US6608155B2 (en) 1997-01-08 2003-08-19 Eastman Chemical Resins, Inc. Metal halide solid acids and supported metal halides as catalysts for the preparation of hydrocarbon resins

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ZA866255B (en) 1987-03-25
EP0214590A3 (fr) 1988-09-14
NO167209C (no) 1991-10-16
NO863561D0 (no) 1986-09-05
NO863561L (no) 1987-03-09
AU572031B2 (en) 1988-04-28
CA1262344A (fr) 1989-10-17
EP0214590A2 (fr) 1987-03-18
JPS6289707A (ja) 1987-04-24
CA1262344C (fr) 1989-10-17
AU6176086A (en) 1987-04-09
ES2001126A6 (es) 1988-04-16
NO167209B (no) 1991-07-08

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